Glass fiber strand



Jan. 15, 1946. BIEFELD 2,392,805

GLASS FIBER STRAND Filed Oct. 11, 1945 I N VEN TOR.

rfrmmeys Patented Jan. 15, 1946 2,392,805 GLASS FIBER STRAND Lawrence P. Biefeld,

Owens-Corning Fiber ration of Delaware Newark, Ohio, assignor to glas Corporation, a corpo- Application October 11, 1943, Serial No. 505,857

12 Claims.

The present invention relates to the production of fibrous glass in strand and other forms. In particular, it is concerned with the binding together and the lubricating of the individual glass fibers in textile strands, slivers and yarns.

In the production of strands of continuous glass fibers, as by the method of the Slayter and Thomas Patent No. 2,300,736, a plurality of streams of molten glass are flowed from a bushing or feederand are attenuated into fine fibers by a rotating drum onto which the fibers are wound. As they are attenuated, the fibers pass over a guide that collects them into a compactstrand and simultaneously applies binding and lubricating materials to the fibers.

The effectiveness of binder and lubricant is to a large extent determinative of the value of the finished strand, yarn or fabric. An improperly lubricated strand is subject to mutual abrasion between the fibers when the strand is flexed, and is quickly self-destroyed. Such a strand also suffers from the abrasion caused by movement through guides and over machine elements as in a loom or braider, by becoming fuzzy due to the breaking of fibers in the strand.

This lubricating effect to separate the fibers and permit their relative movement must be balanced with the directly opposed action of an adhesive binding material that is applied to the strand to hold the individual filaments together securely in the strand. The bound strand must appear as a single fine thread without loose filaments or filament ends. in the unwinding of the strand from the drum on which it was collected during the forming operation. If the strand is not well bound, filaments will separate from the strandduring unwinding and remain on the drum to intertangle with other filaments of the strand until after a, short time further unwinding becomes impossible and all of the strand remaining carded. 1

While thus securely bonding the filaments togather in the strand, it is very important that the binding material permits some relative movement of the filaments in the strand or otherwise the strand will be too brittle to be processed on ordinary textile machines.

Many of these requirements were not met by the prior glass fiber treating materials or only to a ver limited extent. Further, the prior materials were all of such a nature that they were much less permanent thanthe glass fibers and their eflect was lost after only a short while. Being of a wholly organic nature, they had little re- This is most. important on the drum must be dissistance to heat; and they displayed little aflinity for the glass fibers in the presence of water. As a result, under conditions of elevated temperature or in the presence of moisture the glass fiber strands, yarns andtfabrics treated with these prior materials had rather limited resistance to flexing and abrasion.

It is an object of the present invention to increase the strength and the resistance to flexure and abrasion of glass fiber textiles such as strands, yarns and fabrics.

It is a further object to provide a highly permanent lubricating and binding material for glass fiber textiles that has high resistance to heat and to attack by moisture, the field in which glass tion. I

In the prior glass fiber lubricating and binding materials use was made of incompatible substances such as gelatin and oil, starch and oil, etc., to furnish the binding action and the lubrication.

fiber textilesfind applica- With these types of materials the fibers are coated with oil and the gelatin or starch in water tends to collect in droplets on the oiled surface and as a result a uniform coating of binder was not 0btained. There was a tendencyto be unbonded in the strand of their lengths due binder coating.

It is an objectof the present invention to employ a lubricant and binder that are compatible and that are of arelated or similar nature, thus contributing to greater uniformity of the binder and lubricant on the fiber surfaces.

It is a further object of the invention to provide a lubricant and binder that enhance the electrical properties of the finished strands, yarns and fabrics. I

It is a further object of the present invention to provide a heat-resistant lubricant and binder that are compatible with a large number of resins. This aspect of the invention is important where for some filaments for at least parts to the non-uniformity of the the yarns, strands or fabrics are used to reinforce thereby greatly increasing tion of the materials to the fibers.

the coating of the invention to the fibers as they are grouped.

In accordance with my invention, I have discovered that the foregoing objects are realized it the individual fibers in the strand are provided with a coating comprising a combination of compounds selected from the class consisting of hydrolyzable organo-silicanes or silanes, their hydrolysis products and their polymerized hydrolysis products or polysiloxanes, that is, the organosilicon compounds which contain organic groups attached to the silicon atom through direct carbon linkage. At least one of the compounds is a resinous material effective to bind the individual filaments together in the strand, and at least one other of the compounds is a material of oily nature serving tolubricate the filaments to prevent abrasion. I

By hydrolyzable organo-silicanes or silanes is meant'derivatives of SiH4 which contain readily hydrolyzable radicals 1 such as halogens, amino groups, alkoxy, 'aroxy, and acyloxy radicals, etc.,

and organic radicals that are joined to the silicon atoms through carbon atoms. Examples of such organic radicals are as follows: aliphatic radicals, such as methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl to octadecyl and higher; alicyclic radicals such as cyclopentyl, cyclohexyl,

etc.; aryl and alkaryl radicals such as phenyl,

monoand poly-'alkyl phenyls as tolyl, xylyl, mesityl,-mono-, di-, and tri-ethyl phenyls, mono-, di-, and tri-propyl phenyls, etc.; naphthyl, monoand poly-alkyl naphthyls as methyl naphthyl, diethyl naphthyl, tri-propyl naphthyl, etc.; tetrahydronaphthyl, anthracyl, etc.; aralkyl such as benzyl, phenyl-ethyl, etc.; 'alkenyl such as methallyl, allyl,

etc.; and heterocyclic radicals. The above organic radicals may also, if desired, contain inor-' ganic substituents such as halogens, etc.

Hydrolysis oi the above described silicanes produces the corresponding hydrox'y silicanes (sometimes called silicols) which in certain instances may be isolated. However, in most cases, the hydroxy silicanes condense, particularly if heat is applied, toiorm polymers called polysiloxanes which contain one or more Si-O-Si groups.

These polymers may in turn be further polymer 7 ized to higher polymers by suitable treatment such 7 I as by acid, alkali or air. If desired, the hydrolysis product and higher polymers of a mixture of organo-silicanes may be employed in accordance with my invention. The hydrolysis product of such a, mixture is generally akcopolymer which may contain various amounts of differently substituted organo-silicon units. All of these compounds and mixtures, namely, the silanes, their hydrolysis products and thepolysiloxanes are within the scope of my invention as useful fiber coating materials. l

The coating materials of my invention are generally applied in the form of solutions, the nature of the solvent depending upon the specific'characteristics and properties of the compound or compounds involved. Where desired in the interest of economy' and avoidance of fire hazard,

tions.

, Example B v Percent. Phenyl ethyl polysiloxane (resin) 10 Cerese wax 2 Dodecyltrichlorosilicane (lubricant) .5 Stoddard solvent 81 Toluene (originally as. solvent for resin) 4 Hydrogenated vegetable oil 2 Example 0 f 1 Per cent Phenyl ethyl polysiloxane (resin) 5'to .15 Dimethyl pplysiloxaneiresin) 2to '7 it is possible to employ aqueous emulsions of the materials, the water evaporating after applicasuch as a pad, wick, groove, roller, or by spraying 7 or other suitable method. The glass fibers are The concenpassed through the coating material, or films thereof, picking up the proper amount, and producing'a flexible, coherent strand which may be easily wound into a package. Some of the organo-silicone compounds of oily nature may also be applied by being vaporized as by heat, and the vapors brought into contact with the glass fibers.

Although the present invention is of the greatest value when employs-din the manufacture of continuous glass fibers by the mechanical attenuation of molten glass, it is applicable also to the production of glass fibers by other processes, for instance, that disclosed in the Tucker and Lannan Patent No. 2,264,345 of December 2, 1941. The coating material of the invention may also, if desired, be applied as an after-treatment to glass fibers and glass fiber strands and yarns regardless of how produced.

The following examples of coating materials,

representing specific embodiments of the present invention, have been found satisfactory.

Example A Per cent Phenyl ethyl polysiloxane (resin) 5 to 15 Dodecyltrichlorosilicane (lubricant) .01 to 1 Stoddard solvent to The dodecyltrichlorosilicane may be replaced in whole or in part with other organo-silicon derivatives that are of an oily nature, such as long-chain organo silicates, e. g., lauryl silicate, and a high flash coal tar solvent may be employed in place of the Stoddard solvent. Also, other substances may be added in small amounts. For instance, 2 to 10% of wax or vegetable oil may be added where-it is desired to increase the binding effect or the lubricating effect at least temporarily during the forming, twisting and weaving opera- Oct'adecyltrichlorosilicane (lubricant) .2, to 1'7 Hydrogenated vegetable oil lto' 3 Stoddard solvent '70 to 90 Toluene (originally assolvent for resin)- 2 to 6 Other resins may be used, for instance, diphenyl silicon diol, mono ethyl siloxane polymer, mono phenyl or mono ethyl siloxane polymer, mono ethyl-phenyl ethyl ,siloxane copolymers and other organo-silicon compounds that are characterized by being of a resinous nature.

Other lubricants 'found suitable are dodecyl and octadecyl triethy'oxy silicane, and dilauryl 'dichlorosilicane and" dimethyl dichldrosilicane and copolymers of the same,phenyl dodecyl dichlorosilicane, diphenyl dichlorosilicane, phenyl V ethyl dlchlorosilicane, ethyl, methyl or lauryl polysiloxane, lauryl trichlorosilicane or methyl trichlorosilicane or oopolymers of the same, and other'organo-silicon compounds that are characterized by being of an oily nature and there.-

, fore efie'ctive to lubricate the glass film surfaces.

However, those materials are preferred that are derivatives-of long-chain (that is, 12 or more carbon atoms) aliphatic substances. e. g., dodecyltrichlorosilicane and octadecyltrichlorosilicane.

Instead of the compositions of Examples A, B and C, it is sometimes preferable, as in cases where the use of solvents is precluded by cost or other considerations, to employ aqueous systems in which the resin and lubricant are in emulsion form. The following example illustrates this.

Water 83.5 to 94.8

The emulsifying agent may be of any of those commercially available such as those sold under the trade-names, Atlas G9446-E, Aerosol O. T., Santomerse No. 3, and others. The resin and lubricant may be readily emulsified in the water following standard practice. As in'the preceding examples, other materials such as oil, wax and the like may be added if desired.. Also, other organo-silicon resins and other organo-silicon lubricants may be substituted for all or parts of the resin and lubricant in Example D. It has been found, however, that the ethoxy and chloride derivatives are not fully suitable for use in aqueous systems. I

Although it is preferable to apply the lubricant and the resin in admixture to the fibers, they may be applied separately as in the case where the lubricant is applied as a vapor either before or after the resin is applied. Thus, the fibers as they are formed may be passed through a fog or cloud of vaporized organo-silicone lubricant, e. g., dodecyltrichlorosilicane, or ethyl trichlorosilicane, and then passed over a wick or pad which wipes onto the fibers a solution or emulsion of a resinous organo-silicone such as dimethyl polysiloxane.

After the coating materials either in solvents or aqueous emulsions are applied to the fibers, the solvents or water evaporate and leave a small amount of the materials on the fiber surfaces. The organo-silicon resin acts as a binder to cement the fibers together into an integral strand and the organo-silicon lubricant is eiiec- ,tive to prevent mutual abrasion of the fibers in the strand. Glass fiber strands and yarns thus coated have increased strength and their resistance to abrasion and flexing is improved.

This affect on strength and abrasion resistance is especially salutary in the case of glass fibers subjected to moisture as by use at high relative humidity. Whereas previously both strength and abrasion resistance were seriously lowered by the presence of moisture, the present invention has been found to so alter the properties of yarns and fabrics that wet strength and abrasion resistance are in most cases at least as good as the strength and resistance to abrasion under dry conditions. Also, the coating materials of the invention are highly effective in lowering the capillarity of strands and yarns of glass fibers. This is of particular value where the glass fiber strands are employed for electrical insulation since any entry of moisture into the interstices between fibers of the insulation tends to lower dielectric values.

An added advantage of the present invention is that the coating materials are compatible with a large number of resins and, since they also adhere strongly to the fiber surfaces and are not adversely affected by the heat used to cure the resin, the strength of resin-glass fiber combinations such as plastic laminates is markedly bettered.

Referring to the drawing, apparatus for mechanically attenuating molten glass to the form of continuous fine glass fibers is illustrated as may be located to direct a draft of cooling air' onto the streams as they are attenuated.

Intermediate the bushing and the winding spindle a guide I8 is arranged to group the fibers into a strand l9 and to apply coating materials to the fibers as they are grouped. The guide ordinarily comprises a grooved arm 2| covered with a felt pad 22 onto which the coating material is flowed and which wipes the coating material onto the fibers as they are drawn over the pad.

The coating material to be applied to the strand is fed from a container 24 through a suitable feeding tube 25. As shown in the drawing, the guide l8 may be supported on the container by means of resilient arms 26.

A supply of the coating material of the present invention in solution or emulsion is placed in the container 24 and is fed to the pad 22 at a controlled rate so that the desired amount of the material is wiped onto the fibers as they pass over the pad. The rate of feed of the solution of coating material is preferably such that after the evaporation of the solvent from the solution or the water from the emulsion, approximately 1 to 5% coating material by weight of the strand remains on the fibers. This, of course, may be varied within wide limits depending on the. use to which the strand is to be put.

Various modifications may be made within the spirit and scope of the appended claims.

I claim:

1 A fibrous body composed of a multiplicity of glass fibers, the fibers whereof are coated with a material of an oily nature in amounts sufilcient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in amounts suflicient to bind them together into an integral body, both said oily material and said resin containing organo-silicon compounds containing organic groups attached to silicon atoms through direct carbon linkage.

2. A fibrous strand composed of a multiplicity of glass fibers, the fibers whereof are coated with a material of an oily nature in amounts sufficient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in amounts suflicient to bind them together into an integral strand, both said oily material and said resin containing organo-silicon compounds containing organic groups attached to silicon atoms through direct carbon linkage and at least one of the substituents of the material of oily nature being a long-chain aliphatic radical.

3. A fibrous strand composed of a multiplicity of glass fibers, the fibers whereof are coated with a material of an oily nature in amounts sufiicient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in mounts suflicient to bind them together into an integral strand, both said oily material and said resin containing organo-silicon compounds containing organic groups attached to silicon atoms through direct carbon linkage and at least one of the organic groups of the material 7. A fabricated body composed of a multiplicity of glass fibers, the fibers whereof are coated with a material of an oily nature in amount suflicient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in amounts suificient to bind them together resin containing an organo-silicon compound containing organic groups attached to silicon atoms through direct carbon linkage.

5. A fibrous strand composed of a multiplicity of glass fibers, the fibers whereof are coated with a material containing octadecyltrichlorosilicane in amounts sufiicient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in amounts sufficient to bindthem together into an integral body, said resin containing an organo-silicon compound containing organic groups attached to silicon atoms through direct carbon linkage.

6. A textile yarn composed'of a multiplicity-of glass fibers, the fibers whereof are coated with a material of an oily nature in amounts suflicient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in amounts sufficient to bind them together into an integral body, both said oily material and said resin containing organo-silicon compounds the organic substituents of which are radicals selected from the class consisting of alkyl, aryl, alkaryl, and aralkyl' and attached to the silicon atom through direct carbon linkage.

into an integral body, said oily material and said resin both being organo-silicon compounds and one being a silane and the other being a polysiloxane.

8. A fabricated body composed of a multiplicity of glass fibers, the fibers whereof are coated with a material of an oily nature in amount sumcient to lubricate and protect the fiber surfaces against mutual abrasion, and a resin distributed over the fibers in amounts suflicient to bind them together into an integral body, said oily material and said resin both being silanes.

9. A fabricated body composed of a multiplicity of glass fibers, the fibers whereof are coated with comprising phenyl ethyl polysiloxane and octa-V decyltrichlorosilicane.

l2.v As an article of manufacture, a glass fiber strand coated with a material comprising phenyl ethyl polysiloxane and lauryl polysiloxane.

LAWRENCE P. BIEFELD. 

